Organopolysiloxane release resins useful in cooking and baking processes

ABSTRACT

Silanol containing organopolysiloxane resins, especially useful as release resins, prepared by the acetone-water hydrolysis of an organohalosilane blend consisting essentially of about 60 mole percent methyltrichlorosilane, 35 mole percent phenyltrichlorosilane and about 5 mole percent dimethyldichlorosilane, are provided. Cooking utensils, particularly baking utensils coated with the same are also provided.

RELATED APPLICATIONS

This application is a division of application Ser. No. 505,988, filed onSept. 16, 1974, now U.S. Pat. No. 3,925,276 which, in turn is acontinuation-in-part of copending application Ser. No. 115,715, filedFeb. 16, 1971, and now abandoned which, in turn, is acontinuaton-in-part of application Ser. No. 798,187, filed Feb. 10, 1969and now abandoned, which, in turn, is a continuation-in-part ofapplication Ser. No. 671,574, filed Sept. 29, 1967 and now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to organopolysiloxane resins and moreparticularly to organopolysiloxane resins useful as release coatings,particularly in the preparation of cooked and baked goods, especiallysweet baked goods.

With the advent of automation, the baking industry has becomeincreasingly more dependent upon silicone release resin coated bakingutensils. In addition to providing for the easy release of the bakedproduct from the utensil, such as a bread pan, the release coatingserves as a protection against rusting and pitting and also provides fora sanitary baking surface. Moreover, when a set of pans needs servicingby a reglazer, the old coating is generally easily removed with acaustic potash solution.

In the past, however, available silicone release resins have been foundto be quite unsatisfactory, particularly in the baking of sweet goods.The high sugar content in sweet goods, such as cakes, pastries, sweetbreads and the like, rapidly destroys the release properties of theseprior art silicone coatings.

SUMMARY OF THE INVENTION

Accordingly, it is one object of this invention to provide a novelorganopolysiloxane release coating resin.

Another object of this invention is to provide an organopolysiloxanerelease coating resin which is particularly suitable for use in cookingand baking processes.

Still another object of this invention is to provide anorganopolysiloxane release coating resin which is resistant to attackand degradation by sugar and thus especially well suited for use whenbaking sweet goods.

Another object to this invention is to provide a novel process forproviding release properties to cooking utensils, especially bakingutensils.

A still further object of this invention is to provide cooking utensils,particularly baking utensils, which are coated with the novelorganopolysiloxane release resins of this invention.

These and other objects are accomplished herein by providing asilanol-containing organopolysiloxane resin prepared by the processcomprising the steps of:

(i) agitating a mixture comprising (A) an organohalosilane blendconsisting essentially of about 60 mole percent methyltrichlorosilane,about 35 mole percent phenyltrichlorosilane, and about 5 mole percentdimethyldichlorosilane, (B) water, (C) acetone, and (D) awater-immiscible organic solvent, wherein there is present by weight insaid mixture per part by weight of (A), 1.7 to 10 parts of (B), 0.2 to 5parts of (C) and 0.3 to 5 parts of (D); and

(ii) separating the organic solvent solution of (F) from the resultinghydrolysis mixture of step (i), wherein (F) is a silanol-containingorganopolysiloxane resin having an average ratio of about 1.05 organoradicals per silicon atom.

DETAILED DESCRIPTION OF THE INVENTION

In copending application U.S. Ser. No. 115,715, filed Feb. 16, 1971, andnow abandoned there is disclosed a broad class of novel fast curingsilanol-containing organopolysiloxane resins. It has now beensurprisingly discovered that a narrow resin composition within thisbroad class of resins is particularly well suited as a release resincoating for cooking and baking utensils, such as frying pans, pots,bread pans, cookie and pastry sheets, oven trays, etc. It has beendiscovered that this narrow resin composition is highly resistant toattack by charred sugar and thus is particularly well suited as arelease resin in baking processes involving sweet goods.

Thus, the silicon release resin of this invention is prepared byhydrolyzing an organohalosilane blend consisting essentially of about 60mole percent methyltrichlorosilane, about 35 mole percent ofphenyltrichlorosilane and about 5 mole percent of dimethyldichlorosilanein the presence of water, acetone and a water-immiscible organicsolvent. In general, this hydrolysis medium contains from about 1.7parts to 10 parts of water, 0.2 to 5 parts of acetone and 0.3 to 5 partsof said water-immiscible organic solvent per part by weight of thesilane blend.

The various components of the hydrolysis mixture can be addedconcomitantly or separately in any desired order. Generally, theorganohalosilanes are added to the mixture of water, acetone and organicsolvent. Preferably, when this method is used a proportion of from 2 to6 parts of water, about 0.3 to about 2 parts of acetone, and about 0.6to about 2 parts of organic solvent, per part of the total weight oforganohalosilane blend, is employed. It is preferred that theorganohalosilanes are added to the hydrolysis medium, rather than viceversa, as this limits the concentration of hydrochloric acid which isformed during the hydrolysis reaction. A strong hydrochloric acidsolution is undesirable as the hydrochloric acid causes acidpolymerization of the acetone forming polymerization products which addundesirable color to the product and have a deleterious effect on thephysical properties of the product.

A preferred method to prepare the organopolysiloxane release resins ofthis invention is the dual feed process. The dual feed process comprisesfeeding the blend of organohalosilanes (A) and from about 0.9 to 5parts, preferably 0.9 to 1.2 parts of acetone (C) from separatecontainers and through separate conduits, then premixing themimmediately prior to hydrolysis. It is necessary to limit the contacttime if small amounts of water are present in the acetone or in theatmosphere in contact with the organohalosilanes, as the water presentcauses hydrolysis of the organohalosilanes generating acid which causesthe acetone to polymerize. The initial hydrolysis medium prior to theintroduction of the silane blend-acetone mixture contains from about 0to 4.1 parts of acetone (C), preferably from 0.9 to 1.2 parts of acetone(C). The amount of water (B) and organic solvent (D) can be as set forthhereinabove, with preferably from about 3 to 3.5 parts of water (B) and0.9 to 1.2 parts of organic solvent (D) per part of the total weight ofthe blend of organohalosilanes.

The temperature of the hydrolysis mixture can be controlled by the rateof addition of the reagents, or by external heat or by cooling ifdesired. During hydrolysis, a temperature of between about 20° C. toabout 40° C. is preferred. After the addition of all the reagents iscompleted, the mixture is generally agitated for an additional period oftime such as 15 to 30 minutes or more to allow for complete hydrolysisof the organohalosilanes. The mixture is then allowed to settle and theacid aqueous (bottom) layer is drawn off from the organic layer.Depending upon individual desires, the organic layer can then bestripped of solvent to a solids concentration of up to 100%. The organicsolvent may be stripped under reduced pressure or atmospheric pressure.At this point, the resin may be bodied, i.e., build-up of molecularweight, under total reflux, by condensing and cross-linking silanolunits, with the aid of, for example, a catalyst such as iron octoate orCelite (diatomaceous earth) or mixtures thereof, to a desired viscosity,preferably 5-12 cps. at 25° C. at 20% by weight resins solids, Moreover,resin impurities may be removed by filtration, using, for example,filtering aids, such as Celite 545 (diatomaceous earth, sold by JohnsManville), Fuller's earth (calcium montmorillonite), and mixtures of thesame, or simply by centrifugation. The resulting silanol-containingorganopolysiloxane resin has an organo radical to silicon ratio of about1.05 to 1.

Included among the water-immiscible organic solvents used in thepractice of this invention are, for example, hydrocarbons such asbenzene, toluene, xylene and the like; esters such as butyl acetate,ethyl acetate, ethers such as diethylether and the like. Toluene is mostpreferred. In general, however, any water-immiscible organic solvent,which is inert to the hydrolysis reactants during hydrolysis and inwhich the hydrolyzate is soluble to provide for its separation from theaqueous layer, may be used.

In another embodiment of the present invention the silanol-containingorganopolysiloxane resin of the present invention, as describedhereinabove, is readily formulated into a desirable release resincoating mixture. In doing so, the organopolysiloxane resin is merelyadmixed with conventional solvents, curing catalysts, silicone fluids,film-forming aids, etc. Resulting from their primary intended use infood cooking and baking processes, it is preferred, of course, thatthese release resin formulation components be acceptable food contactadditives. Thus, suitable solvents include, for example, toluene, xyleneand the like; suitable silicone fluids include, for example,conventional fluids which are generally mixtures ofmethylphenylsiloxanes, dimethylsiloxanes and/ordiphenyldimethylsiloxanes. An acceptable curing catalyst is, forexample, iron octoate. Film-forming aids which are suitable for thepurposes of this invention include, for example, glycol ethers, such asbutyl Cellosolve (ethylene glycol monobutylether), naphtha, ketones,acetates and the like and mixtures thereof. Other film-forming aidswould, of course, include any organic solvent of sufficient volatilityand stability to aid in the formation of a film.

The amounts of the materials which are employed in these release resinformulations may vary within wide limits. In general, however, theorganopolysiloxane resin is employed in an amount ranging from about 15to about 30 percent of the total formulation, preferably about 20percent. The organosilicone fluids, such as those described hereinabove,generally comprise from about 1 to 3%, while the curing catalyst ispresent in amounts which can vary, for example, from about 0.03 to about1.8%, preferably about 0.06%, based upon the resin solids content. Theamount of other additives generally employed, such as film-formingadditives, can also vary within wide limits, depending upon individualrequirements, and such amounts are readily ascertainable by those ofordinary skill in the art.

In another embodiment of this invention, the organopolysiloxane releaseresin coating mixtures described above are readily applied byconventional techniques, such as spraying, dipping, brushing, etc., onthe food contact surface or surfaces of, for example, glass, ceramic ormetal cooking and baking utensils such as frying pans, pots, bread pans,oven trays, cookie sheets, toaster oven trays and the like. Simply heatcuring these organopolysiloxane release resin coatings, afterapplication, provides the cooking or baking utensil with not only ahighly sugar-resistant coating but moreover a coating which is highlysolvent-resistant in addition to being resistant to grease and fats. Thethickness of the coating necessary to provide the desired releaseproperties varies and is generally from about .035 to 0.5 mils.

In order that those skilled in the art may better understand how topractice the present invention, the following examples are given by wayof illustration and not by way of limitation. All parts are by weight.

EXAMPLE I

This example illustrates the preparation of a silanol-containingorganopolysiloxane release resin and release resin coating mixtureaccording to this invention.

There are charged to a reaction flask equipped with a condenser,agitator and thermometer, 3000 parts of water, 900 parts of toluene and900 parts of acetone. There are added to the mixture in the reactionflask in dual feed with 900 parts of acetone through a common dip leg, asilane blend consisting of 526 parts of methyltrichlorosilane, 436 partsof phenyltrichlorsilane, and 38 parts of dimethyldichlorosilane. Therate of addition is controlled for 30 minutes maintaining the peakreaction temperature below 45° C. The mixture is stirred for 15 minutes,and allowed to settle for 15 minutes. The acid water (bottom) layer isdrawn off and discarded. Ten percent water based on resin solids ischarged to the resin layer and the mixture is agitated for 5 minutes,and settled for 15 minutes. The excess water is drawn off and discarded.The washed hydrolyzate is filtered through a mixture of Celite 545 andFuller's earth. The filtered hydrolyzate is atmospherically stripped to120° C. One percent Celite 545 based on resin solids is added to theresin concentrate and the solvent is stripped off to 140° C. totalreflux. The condensate is trapped off and the resin is bodied at about160° C. in the presence of iron octoate to an endpoint to give a finalviscosity of 9-12 centipoise (cps) at 25° C. on an LVF BrookfieldViscometer at 20% solids.

A release resin solution is made from the above organopolysiloxane resinas follows:

    ______________________________________                                        Resin dissolved in equal parts of xylene                                                               160    parts                                         Xylene                   84     "                                             Butyl Cellosolve         32     "                                             Naphtha 9300 (available from Union Amsco,                                                              120    "                                             California)                                                                   Iron octoate             0.8    "                                             General Electric silicone fluid 81950                                          (a mixture of methylphenylsiloxanes,                                          dimethylsiloxanes and diphenyl                                                dimethyl siloxanes)     3.7                                                  ______________________________________                                    

A tin coated steel cup is flood-coated with the resin solution andair-dried for 30 minutes. The cup is placed on a preheated 425° F. ovenfor one hour. After cooling, a sugar cube is placed in the cup and wetwith twenty-five drops of water. The cup is placed in a 425° F. oven for45 minutes. The cup is cooled to room temperature and checked forrelease of the charred sugar. The charred sugar does not adhere to theresin coating.

For comparative purposes, silanol-containing organopolysiloxane resinsand release resin coating mixtures are prepared according to ExamplesII-V.

EXAMPLE II

There is charged to a reaction flask equipped with a condenser,agitator, and thermometer 6000 parts of water, 1350 parts of acetone,and 1350 parts of toluene. There is added to the mixture in the reactionflask in a dual feed with 1350 parts of acetone through a common dip leg1500 parts of phenyltrichlorosilane. The rate of addition is controlledfor 20 minutes, controlling the peak reaction temperature below 40° C.The mixture is stirred for 15 minutes and settled for 15 minutes. Theacid water (lower) layer is drawn off and discarded. The solvent isremoved under reduced pressure to 55-65% resin solids. The hydrolyzateconcentrate is filtered through a mixture of diatomaceous earth andFuller's earth. The filtered concentrate is further stripped underreduced pressure to 95-100% solids. The hot melt is cast and cooled in atray. Upon cooling, the resin is solid and friable.

A release resin solution is made from the above resin as follows:

    ______________________________________                                        Resin dissolved in equal parts of xylene                                                               160    parts                                         Xylene                   84     "                                             Butyl Cellosolve         32     "                                             Naphtha 9300             120    "                                             Iron Octoate             0.8    "                                             General Electric 81950 silicone fluid                                                                  3.7    "                                             ______________________________________                                    

A tin coated steel cup is flood-coated with the resin solution,air-dried 30 minutes. The cup is placed in a preheated 425° F. oven forone hour. After cooling, a sugar cube is placed in the cup and wet withtwenty-five drops of water. The cup is placed in a 425° F. oven for 45minutes. The cup is cooled to room temperature and checked for releaseof the charred sugar. The charred sugar sticks tenaciously to thesilicone coating. It cannot be removed without destroying the coating.

EXAMPLE III

There is charged to a flask equipped with a condenser, agitator andthermometer 3000 parts of water, 900 parts of toluene, and 900 parts ofacetone. There is added to the mixture in the reaction flask a silaneblend consisting of 414 parts of methyltrichlorosilane and 586 parts ofphenyltrichlorosilane in a dual feed through a common dip leg with 900parts of acetone. The rate of addition is controlled for 30 minutes,controlling the peak reaction temperature below 30° C. The mixture isagitated for 15 minutes, settled for 15 minutes. The acid water (bottom)layer is drawn off and discarded. Ten percent water based on resinsolids is added to the hydrolyzate and the mixture is agitated for fiveminutes. The water and solvent are removed under reduced pressure to55-70% solids concentrate. The resin concentrate is filtered through amixture of Celite 545 and Fuller's earth. The remaining solvent isremoved under reduced pressure to 130° C. and 98-100% solids. The hotmelt is cast in a tray and cooled. Upon cooling, the resin is hard andfriable. A release resin solution is made from the resin and tested ascutlined in Example II. The charred sugar cannot be removed withoutdestroying the resin film.

EXAMPLE IV

A silanol-containing organopolysiloxane resin and release resin coatingmixture is made, as described in Example II, from allmethyltrichlorosilane. The resin coating mixture is tested for sugarresistance as in Example II. The sugar cannot be removed withoutdestroying the resin film.

EXAMPLE V

A silanol-containing organopolysiloxane resin and release resin coatingmixture is made, as described in Example II, from a 50% by weight blendof diphenyldichlorosilane and 50% by weight of dimethyldichlorosilane.The resin coating mixture is tested for sugar resistance as in ExampleII. The sugar cannot be removed without destroying the resin film.

From the above Examples, it is clearly seen that only thesilanol-containing organopolysiloxane release resin of Example I isresistant to sugar degradation.

Obviously, other modifications and variations of the present inventionare possible in light of the above teachings. It is therefore to beunderstood that changes may be made in the particular embodiments ofthis invention which are within the full intended scope of the inventionas defined by the appended claims.

What is claimed and desired to be received by Letters Patent is:
 1. Acooking utensil comprising an interior cooking surface having coatedthereon a silanol-containing organopolysiloxane resin said resinprepared by the process comprising the steps ofi. agitating a mixturecomprising (A) an organohalosilane blend consisting essentially of about60 mole percent methyltrichlorosilane, about 35 mole percentphenyltrichlorosilane, and about 5 mole percent dimethyldichlorosilane,(B) water, (C) acetone, and (D) a water-immiscible organic solvent,wherein there is present by weight in said mixture per part by weight of(A), about 1.7 to about 10 parts of (B), about 0.2 to about 5 parts of(C), and about 0.3 to about 5 parts of (D); and ii. separating theorganic solvent solution of (F) from the resulting hydrolysis mixture ofstep (i), wherein (F) is a silanol-containing organopolysiloxane resinhaving an average ratio of about 1.05 organic radicals per silicon atom.2. A cooking utensil comprising an interior cooling surface havingcoated thereon the silanol-containing organopolysiloxane resin definedin claim 1, said water (B) being present in an amount of from about 2 toabout 6 parts, said acetone (C) being present in an amount of from about0.3 to about 2 parts, and said water-immiscible solvent (D) beingpresent in an amount of from about 0.6 to about 2 parts, per part byweight of said organohalosilane blend (A).
 3. A cooking utensilcomprising an interior cooking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim 1 whereinsaid water-immiscible organic solvent is toluene.
 4. A cooking utensilcomprising an interior cooking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim 1 whereincomponent (F) is bodied to a desired viscosity of from about 5-12centipoise at 25° C at 20% by weight solids.
 5. A cooking utensilcomprising an interior cooking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim 1 whereinsaid organohalosilane blend (A) is premixed with from about 0.9 to about5 parts by weight of acetone immediately prior to hydrolysis in theremainder of the hydrolysis mixture comprising from about 0 to 4.1 partsof acetone (C), about 1.7 to about 10 parts water (B), and from about0.3 to about 5 parts water-immiscible organic solvent (D).
 6. A cookingutensil comprising an interior cooking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim 5 whereinsaid organohalosilane blend (A) is premixed with from about 0.9 to 1.2parts of acetone (C) immediately priior to hydrolysis in the remainderof the hydrolysis mixture comprising from about 0.9 to about 1.2 partsof acetone (C), from about 3 to about 3.5 parts water (B) and from about0.9 to 1.2 parts of water-immiscible organic solvent (D).
 7. A cookingutensil comprising an interior cooking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim 5 whereinsaid water-immiscible organic solvent is toluene.
 8. A cooking utensilcomprising an interior cooking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim 6 whereincomponent (F) is bodied to a desired viscosity of from about 5-12centipoise at 25° C at 20% by weight resins solid.
 9. A baking utensilcomprising an interior baking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim
 1. 10. Abaking utensil comprising an interior baking surface having coatedthereon the silanol-containing organopolysiloxane resin defined in claim2.
 11. A baking utensil comprising an interior baking surface havingcoated thereon the silanol-containing organopolysiloxane resin definedin claim
 3. 12. A baking utensil comprising an interior baking surfacehaving coated thereon the silanol-containing organopolysiloxane resindefined in claim
 4. 13. A baking utensil comprising an interior bakingsurface having coated thereon the silanol-containing organopolysiloxaneresin defined in claim
 5. 14. A baking utensil comprising an interiorbaking surface having coated thereon the silanol-containingorganopolysiloxane resin defined in claim
 6. 15. A baking utensilcomprising an interior baking surface having coated thereon thesilanol-containing organopolysiloxane resin defined in claim
 7. 16. Abaking utensil comprising an interior baking surface having coatedthereon the silanol-containing organopolysiloxane resin defined in claim8.
 17. A method of providing surface release properties to a cookingutensil comprising applying the organopolysiloxane release resin definedin claim 1 in admixture with a material selected from the groupconsisting of a organic solvent, an organosilicone fluid, a film-formingaid, a curing agent and mixtures thereof to an interior cooking surfaceof said cooking utensil and thereafter curing said admixture.
 18. Amethod of providing surface release properties to a cooking utensilcomprising applying the organopolysiloxane release resin defined inclaim 2 in admixture with a material selected from the group consistingof an organic solvent, an organosilicone fluid, a film-forming aid, acuring agent and mixtures thereof to an interior cooking surface of saidcooking utensil and thereafter curing said admixture.
 19. A method ofproviding surface release properties to a cooking utensil comprisingapplying the organopolysiloxane release resin defined in claim 4 inadmixture with a material selected from the group consisting of anorganic solvent, an organosilicone fluid, a film-forming aid, a curingagent and mixtures thereof to an interior cooking surface of saidcooking utensil and thereafter curing said admixture.
 20. A method ofproviding surface release properties to a cooking utensil comprisingapplying the organopolysiloxane release resin defined in claim 5 inadmixture with a material selected from the group consisting of anorganic solvent, an organosilicone fluid, a film-forming aid, a curingagent and mixtures thereof to an interior cooking surface of saidcooking utensil and thereafter curing said admixture.
 21. A method ofproviding surface release properties to a cooking utensil comprisingapplying the organopolysiloxane release resin defined in claim 6 inadmixture with a material selected from the group consisting of anorganic solvent, an organosilicone fluid, a film-forming aid, a curingcatalyst and mixtures thereof to an interior cooking surface of saidcooking utensil and thereafter curing said admixture.
 22. A method ofproviding surface release properties to a cooking utensil comprisingapplying the organopolysiloxane release resin defined in claim 7 inadmixture with a material selected from the group consisting of anorganic solvent, an organosilicone fluid, a film-forming aid, a curingcatalyst and mixtures thereof to an interior cooking surface of saidcooking utensil and thereafter curing said admixture.
 23. A method ofproviding surface release properties to a cooking utensil comprisingapplying the organopolysiloxane release resin defined in claim 8 inadmixture with xylene, an organosilicone fluid comprising a mixture ofmethylphenylsiloxanes, dimethylsiloxanes and diphenylmethylsiloxanes,naphtha, ethylene glycol monobutylether and iron octoate to an interiorcooking surface of said cooking utensil and thereafter curing saidadmixture.
 24. A method of providing surface release properties to abaking utensil comprising applying the organopolysiloxane release resindefined in claim 1 in admixture with a material selected from the groupconsisting of an organic solvent an organosilicone fluid, a film-formingaid, a curing agent and mixtures thereof to a interior baking surface ofsaid baking utensil and thereafter curing said admixture.
 25. A methodof providing surface release properties to a baking utensil comprisingapplying the organopolysiloxane release resin defined in claim 2 inadmixture with a material selected from the group consisting of anorganic solvent, an organosilicone fluid, a film-forming aid, a curingagent and mixtures thereof to an interior baking surface of said bakingsurfaces of said baking utensil and thereafter curing said admixture.26. A method of providing surface release properties to a baking utensilcomprising applying the organopolysiloxane release resin defined inclaim 4 in admixture with a material selected from the group consistingof a organic solvent, an organosilicone fluid, a film-forming aid, acuring agent and mixtures thereof to a interior baking surface of saidbaking utensil and thereafter curing said admixture.
 27. A method ofproviding surface release properties to a baking utensil comprisingapplying the organopolysiloxane release resin defined in claim 5 inadmixture with a material selected from the group consisting of anorganic solvent, an organosilicone fluid, a film-forming aid, a curingagent and mixtures thereof to an interior baking surface of said bakingutensil and thereafter curing said admixture.
 28. A method of providingsurface release properties to a baking utensil comprising applying theorganopolysiloxane release resin defined in claim 6 in admixture with amaterial selected from the group consisting of a organic solvent, anorganosilicone fluid, a film-forming aid, a curing catalyst and mixturesthereof to an interior baking surface of said baking utensil andthereafter curing said admixture.
 29. A method of providing surfacerelease properties to a baking utensil comprising applying theorganopolysiloxane release resin defined in claim 7 in admixture with amaterial selected from the group consisting of a organic solvent, anorganosilicone fluid, a film-forming aid, a curing catalyst and mixturesthereof to an interior baking surface of said baking utensil andthereafter curing said admixture.
 30. A method of providing surfacerelease properties to a baking utensil comprising applying theorganopolysiloxane release resin defined in claim 8 in admixture withxylene, an organosilicone fluid comprising a mixture ofmethylphenylsiloxanes, dimethylsiloxanes and diphenylmethylsiloxanes,naphtha, ethylene glycol monobutylether and iron octoate to an interiorbaking surface of said baking utensil and thereafter curing saidadmixture.
 31. A cooking utensil comprising an interior cooking surfacehaving coated and cured thereon a silanol-containing organopolysiloxaneresin, said resin prepared by the process comprising the stepsofagitating a mixture comprising (A) an organohalosilane blendconsisting essentially of about 60 mole percent methyltrichlorosilane,about 35 mole percent phenyltrichlorosilane, and about 5 mole percentdimethyldichlorosilane, (B) water, (C) acetone, and (D) awater-immiscible organic solvent, wherein there is present by weight insaid mixture per part by weight of (A), about 1.7 to about 10 parts of(B), about 0.2 to about 5 parts of (C), and about 0.3 to about 5 partsof (D); and ii. separating the organic solvent solution of (F) from theresulting hydrolysis mixture of step (i), wherein (F) is asilanol-containing organopolysiloxane resin having an average ratio toabout 1.05 organic radicals per silicon atom.
 32. A baking utensilcomprising an interior baking surface having coated and cured thereonthe silanol-containing organopolysiloxane resin defined in claim 3.